WO2011056813A1 - Nouvelles électrodes et batteries rechargeables - Google Patents

Nouvelles électrodes et batteries rechargeables Download PDF

Info

Publication number
WO2011056813A1
WO2011056813A1 PCT/US2010/055204 US2010055204W WO2011056813A1 WO 2011056813 A1 WO2011056813 A1 WO 2011056813A1 US 2010055204 W US2010055204 W US 2010055204W WO 2011056813 A1 WO2011056813 A1 WO 2011056813A1
Authority
WO
WIPO (PCT)
Prior art keywords
silver
stabilizing agent
rechargeable battery
cathode
powder
Prior art date
Application number
PCT/US2010/055204
Other languages
English (en)
Inventor
Hongxia Zhou
George W. Adamson
Original Assignee
Zpower, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zpower, Inc. filed Critical Zpower, Inc.
Priority to EP10776246.0A priority Critical patent/EP2497138B1/fr
Priority to CA2779090A priority patent/CA2779090A1/fr
Priority to US13/504,986 priority patent/US9184444B2/en
Priority to JP2012537205A priority patent/JP5806675B2/ja
Publication of WO2011056813A1 publication Critical patent/WO2011056813A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/34—Silver oxide or hydroxide electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/32—Silver accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/54—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of silver
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This invention relates to a novel cathode formed by mixing a stabilizing agent with a cathode active material to form an electrode having improved properties over traditional cathodes.
  • Rechargeable batteries are known in the art and commonly used, for example, in portable electronic devices. Although conventional rechargeable batteries are useful, the systems and methods used to recharge the batteries are nevertheless susceptible to improvements that may enhance or improve their service life, shelf life, and/or performance.
  • the anode When a traditional battery is discharged, the anode supplies positive ions to an electrolyte and electrons to an external circuit.
  • the cathode is typically an electronically conducting host into which positive ions are inserted reversibly from the electrolyte as a guest species and are charge-compensated by electrons from the external circuit.
  • a secondary battery, or cell uses a reaction that can be reversed when current is applied to the battery; thus, “recharging" the battery.
  • the chemical reactions at the anode and cathode of a secondary battery must be reversible.
  • the present invention provides a novel cathode material that comprises silver that is associated with one or more particles of a stabilizing agent, wherein the one or more particles of stabilizing agent have a diameter or mean diameter of less than about 250 run (e.g., about 100 nm or less).
  • One aspect of the present invention provides a cathode for use in a rechargeable battery comprising a cathode active material comprising a stabilizing agent comprising a powder having a mean particle diameter of about 250 nm or less (e.g., about 100 nm or less); and silver, wherein the stabilizing agent is present in an amount sufficient to impart the cathode with a Coulombic efficiency of greater than about 98 %.
  • the cathode active material comprises silver
  • the silver comprises Ag, AgO, AgzO, Ag 2 0 3 , AgOH, Ag(OH) 2 , Ag(OH) 3 , AgOOH, AgONa, AgOK, AgOLi, AgORb, AgOONa, AgOOK, AgOOLi, AgOORb, AgCu0 2 , AgFe0 2 , AgMnCh, Ag 2 CuMn0 4 , any hydrate thereof, or any combination thereof.
  • the silver further comprises Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is doped with a first dopant comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is doped with a first dopant comprising Ga.
  • silver is coated with a coating agent comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is coated with a coating agent comprising Pb.
  • the silver is doped with a first dopant comprising Ga, and the silver is coated with a coating agent comprising Pb.
  • the stabilizing agent comprises a powder comprising a p- type semiconductor, an n-type semiconductor, or any combination thereof.
  • the stabilizing agent comprises a powder comprising ZnO, S1O 2 , ⁇ 2, T1O 2 , AI 2 O3, MgO, SiC, ⁇ 2 0 3 , H02O3, ZnTi0 3 , B 2 0 3 , LiAl0 2 , BaTi0 3 , Li ⁇ xCa ⁇ SiO ⁇ LL ⁇ MgxSiO ⁇ Bi 2 0 3 , ⁇ 13 ⁇ 40 3 , MnOz, Ultramarine, or any combination thereof, wherein x is 1-4.
  • the stabilizing agent comprises a powder comprising ZnO.
  • the ZnO is doped with a second dopant comprising A1 2 0 3 , iron oxide, indium oxide, or any combination thereof.
  • the ZnO is doped with a second dopant comprising A1 2 0 3 .
  • the stabilizing agent comprises a powder comprising ⁇ 1 ⁇ 2 ⁇
  • the stabilizing agent comprises a powder comprising Si0 2 .
  • the stabilizing agent comprises a powder, and the powder comprises a plurality of particles comprising SiO ⁇ Zr0 2 , and ZnO.
  • the stabilizing agent comprises a powder comprising Si0 2 particles, Z1O2 particles, and ZnO particles.
  • the ZnO particles are doped with a second dopant comprising A1 2 0 3 .
  • the ZnO particles comprise from about 1 wt% to about 10 wr of AI2O3 by weight of the ZnO particles.
  • the cathode active material comprises about 0.5 wt % or less (e.g., about 0.2 wt % or less) of the stabilizing agent.
  • the cathode active material comprises from about 0.01 wt % to about 0.3 wt % (e.g., from about 0.01 wt % to about 0.2 wt %) of the stabilizing agent.
  • the cathode further comprises a binder.
  • the cathode comprises a binder comprising PTFE.
  • Another aspect of the present invention provides a rechargeable battery comprising a cathode comprising a cathode active material comprising silver and a stabilizing agent; an anode comprising zinc; and an electrolyte, wherein the stabilizing agent comprises a powder having a mean particle diameter of about 250 nm or less (e.g., about 100 nm or less), the silver associates with one or more particles of the stabilizing agent, and the stabilizing agent is present in an amount sufficient to impart the cathode with a Coulombic efficiency of greater than about 98 %.
  • the silver comprises Ag, AgO, Ag 2 0, Ag 2 0 3 , AgOH, Ag(OH) 2 , Ag(OH) 3 , AgOOH, AgONa, AgOK, AgOLi, AgORb, AgOONa, AgOOK, AgOOLi, AgOORb, AgCuO ⁇ AgFe0 2 , AgMnO ⁇ Ag 2 CuMn04, any hydrate thereof, or any combination thereof.
  • the silver further comprises Fb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is doped with a first dopant comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is doped with a first dopant comprising Ga.
  • the silver is coated with a coating agent comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is coated with a coating agent comprising Pb.
  • the silver is coated with a coating agent comprising Pb, and the silver is doped with a first dopant comprising Ga.
  • the stabilizing agent comprises a powder comprising a p- type semiconductor, an n-type semiconductor, or any combination thereof.
  • the stabilizing agent comprises a powder comprising ZnO, S1O2, Zr0 2 , TiO ⁇ Al 2 0 3 , MgO, SiC, ln 2 0 3 , Ho 2 0 3 , ZnTi0 3 , B 2 0 3 , LiA10 2 , BaTi0 3 , Li4-xCa x Si0 4 , Li 4-» Mg x Si0 4 , Bi 2 0 3 , ⁇ 1 ⁇ 40 3 , Mn0 2 , Ultramarine, or any combination thereof, wherein x is 1-4.
  • the stabilizing agent comprises a powder comprising ZnO.
  • the ZnO is doped with a second dopant comprising A1 2 0 3 , iron oxide, indium oxide, or any combination thereof.
  • the ZnO is doped with a second dopant comprising AI2O3.
  • the stabilizing agent comprises a powder comprising Zr0 2 .
  • the stabilizing agent comprises a powder comprising S1O2.
  • the stabilizing agent comprises a powder, and the powder comprises a plurality of particles comprising S1O2, ⁇ 2, and ZnO.
  • the stabilizing agent comprises a powder comprising S1O2 particles, ⁇ 2 particles, and ZnO particles.
  • the ZnO particles are doped with a second dopant comprising AI2O3.
  • the ZnO particles comprise from about 1 wt% to about 10 wt% of AI2O3 by weight of the ZnO particles.
  • the cathode active material comprises about 7 wt % or less (e.g., about 0.5 wt % or less) of the stabilizing agent.
  • the cathode active material comprises from about 0.01 wt % to about 0.3 wt % (e.g., from about 0.01 wt % to about 0.2 wt ) of the stabilizing agent.
  • the cathode further comprises a binder.
  • the cathode further comprises a binder, and the binder comprises PTFE.
  • an electrochemical cell comprising a cathode comprising a cathode active material comprising silver and a stabilizing agent; an anode comprising Zn; and an electrolyte
  • the stabilizing agent comprises a powder having a mean particle diameter of about 250 nm or less (e.g., about 100 nm or less)
  • the silver is associated with at least one particle of a stabilizing agent
  • the cathode active material comprises a sufficient amount of stabilizing agent such that the cell retains a substantially constant charge capacity after more than about 70 charge cycles.
  • the silver comprises Ag, AgO, Ag 2 0, Ag 2 0 3 , AgOH, Ag(OH) 2 , Ag(OH) 3 , AgOOH, AgONa, AgOK, AgOLi, AgORb, AgOONa, AgOOK, AgOOLi, AgOORb, AgCu0 , AgFe0 2 , AgMn0 2 , Ag 2 CuMn04, any hydrate thereof, or any combination thereof.
  • the silver further comprises Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is doped with a first dopant comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is coated with a coating agent comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is coated with a coating agent comprising Pb.
  • the silver is coated with a coating agent comprising Pb, and the silver is doped with a first dopant comprising Ga.
  • the stabilizing agent comprises a powder comprising a p- type semiconductor, an n-type semiconductor, or any combination thereof.
  • the stabilizing agent comprises a powder comprising ZnO, S1O2, Zr0 2 , T1O2, A1 2 0 3 , MgO, SiC, ln 2 0 3 , H02O3, ZnTi0 3 , B 2 0 3 , L1AIO2, BaTi0 3 , Li4.,Ca x Si0 4 , LU-xMgxSiO Bi 2 0 3 , ⁇ 13 ⁇ 40 3 , Mn0 2 , Ultramarine, or any combination thereof, wherein x is 1-4.
  • the stabilizing agent comprises a powder comprising ZnO.
  • the ZnO is doped with a second dopant comprising AhQj, iron oxide, indium oxide, or any combination thereof.
  • the ZnO is doped with a second dopant comprising A1 2 0 3 .
  • the stabilizing agent comprises a powder comprising Zrt-h.
  • the stabilizing agent comprises a powder comprising Si0 2 .
  • the stabilizing agent comprises a powder, and the powder comprises a plurality of particles comprising Si0 2 , ⁇ 2, and ZnO.
  • the stabilizing agent comprises a powder comprising Si0 2 particles, Zr0 2 particles, and ZnO particles.
  • the ZnO particles are doped with a second dopant comprising A1 2 0 3 .
  • the ZnO particles comprise from about 1 wt% to about 10 wt% of A1 2 0 3 by weight of the ZnO particles.
  • the cathode active material comprises about 7 wt % or less (e.g., about 0.5 wt % or less or about 0.2 wt % or less ) of the stabilizing agent.
  • the cathode active material comprises from about 0.01 wt % to about 0.3 wt % (e.g., from about 0.01 wt % to about 0.2 wt %) of the stabilizing agent.
  • Another aspect of the present invention provides a rechargeable battery comprising a cathode comprising a cathode active material comprising silver and a stabilizing agent; an anode comprising zinc; and an electrolyte, wherein the stabilizing agent comprises a powder having a mean particle diameter of about 250 nm or less (e.g., about 100 run or less), and the rechargeable battery provides at least about 200 mAh/g of silver per discharge for a period of at least about 100 consecutive charge cycles.
  • the stabilizing agent comprises a powder having a mean particle diameter of about 250 nm or less (e.g., about 100 run or less)
  • the rechargeable battery provides at least about 200 mAh/g of silver per discharge for a period of at least about 100 consecutive charge cycles.
  • the battery provides at least about 200 mAh/g of silver per discharge for a period of at least about 120 consecutive charge cycles. In other embodiments, the battery provides more than about 200 mAh/g of silver per discharge for a period of at least about 100 consecutive charge cycles. And, in some embodiments, the battery provides at least about 20 Ah/g of silver of aggregate capacity over a period of no more than about 250 consecutive charge cycles.
  • the silver comprises Ag, AgO, Ag 2 0, Ag 2 0 3 , AgOH, Ag(OH) 2 , Ag(OH) 3 , AgOOH, AgONa, AgOK, AgOLi, AgORb, AgOONa, AgOOK, AgOOLi, AgOORb, AgCu0 2 , AgFe0 2 , AgMn02, Ag 2 CuMn0 4 , any hydrate thereof, or any combination thereof.
  • the silver further comprises Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is doped with a first dopant comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is coated with a coating agent comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is coated with a coating agent comprising Pb.
  • the silver is coated with a coating agent comprising Pb, and the silver is doped with a first dopant comprising Ga.
  • the stabilizing agent comprises a powder comprising a p- type semiconductor, an n-type semiconductor, or any combination thereof.
  • the stabilizing agent comprises a powder comprising ZnO, SiO_, Zr02, T1O2, AI2O3, MgO, SiC, In 2 Oj, H02O3, ZnTiC , B 2 0 3 , ⁇ 2, BaTi0 3 , Li ⁇ CaxSiO,,, Li4.
  • the stabilizing agent comprises a powder comprising ZnO.
  • the ZnO is doped with a second dopant comprising AI2O3, iron oxide, indium oxide, or any combination thereof.
  • the ZnO is doped with a second dopant comprising AI2O3.
  • the stabilizing agent comprises a powder comprising Z1O2.
  • the stabilizing agent comprises a powder comprising S1O2.
  • the stabilizing agent comprises a powder, and the powder comprises a plurality of particles comprising Si0 2 , ZrC ⁇ , and ZnO.
  • the stabilizing agent comprises a powder comprising Si0 2 particles, Zr0 2 particles, and ZnO particles.
  • the ZnO particles are doped with a second dopant comprising AI2O3.
  • ZnO particles are doped with from about 1 wt% to about 10 wt% of a second dopant comprising AI 2 O3 by weight of the ZnO particles.
  • the cathode active material comprises about 7 wt % or less (e.g., about 0.5 wt% or less) of the stabilizing agent.
  • the cathode active material comprises from about 0.01 wt % to about 0.3 wt % (e.g., from about 0.01 wt % to about 0.2 wt%) of the stabilizing agent.
  • the cathode material further comprises a binder, such as PTFE.
  • Another aspect of the present invention provides a rechargeable battery comprising a cathode comprising a cathode active material comprising silver and a stabilizing agent; an anode comprising zinc; and an electrolyte, wherein the stabilizing agent comprises a powder having a mean particle diameter of about 250 nm or less (e.g., about 100 nm or less), and the rechargeable battery provides a battery capacity of at least about 140 mAh/g of silver per discharge for a period of at least aboutlOO consecutive charge cycles.
  • the battery provides a battery capacity of at least about 140 mAh/g of silver per discharge for a period of at least about 150 consecutive charge cycles.
  • the battery provides a battery capacity of more than about 140 mAh/g of silver per discharge for a period of at least about 100 consecutive charge cycles. In some embodiments, the battery provides at least about 14 Ah/g of silver aggregate capacity over a period of no more than about 1000 consecutive charge cycles. And, in other embodiments, the battery provides at least about 200 mAh/g of silver per discharge for a period of at least about 150 consecutive charge cycles.
  • the silver comprises Ag, AgO, Ag 2 0, Ag 2 ⁇ 1 ⁇ 4, AgOH, Ag(OH) 2 , Ag(OH) 3 , AgOOH, AgONa, AgOK, AgOLi, AgORb, AgOONa, AgOOK, AgOOLi, AgOORb, AgCu0 2 , AgFe0 2 , AgMn(3 ⁇ 4, Ag 2 CuMn0 4 , any hydrate thereof, or any combination thereof.
  • the silver further comprises Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is doped with a first dopant comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is coated with a coating agent comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is coated with a coating agent comprising Pb.
  • the silver is coated with a coating agent comprising Pb, and the silver is doped with a first dopant comprising Ga.
  • the stabilizing agent comprises a powder comprising a retype semiconductor, an n-type semiconductor, or any combination thereof.
  • the stabilizing agent comprises a powder comprising ZnO, Si0 2 , ⁇ 2, T1O2, AI2O3, MgO, SiC, ln 2 0 3 , H02O3, ZnTi0 3 , B2O3, LiAlCh, BaTi0 3 , LL Ca ⁇ SiO ⁇ Li4-xMg x Si0 , Bi 2 0 3 , Yb 2 0 3 , Mn0 2 , Ultramarine, or any combination thereof, wherein x is 1-4.
  • the stabilizing agent comprises a powder comprising ZnO.
  • the ZnO is doped with a second dopant comprising A1 2 0 3 , iron oxide, indium oxide, or any combination thereof. In some instances, the ZnO is doped with a second dopant comprising A 0 3 .
  • the stabilizing agent comprises a powder comprising Z1O2.
  • the stabilizing agent comprises a powder comprising S1O2.
  • the stabilizing agent comprises a powder, and the powder comprises a plurality of particles comprising Si0 2 , Z1O2, and ZnO. In other examples, the stabilizing agent comprises a powder comprising S1O2 particles, Z1O2 particles, and ZnO particles.
  • the ZnO particles are doped with a second dopant comprising A1 2 0 3 . In other instances, the ZnO particles comprise from about 1 wt% to about 10 wt% of A1 2 0 3 by weight of the ZnO particles.
  • the cathode active material comprises about 0.5 wt % or less (e.g., about 0.2 wt % or less) of the stabilizing agent. For example, the cathode active material comprises from about 0.01 wt % to about 0.3 wt % (e.g., from about 0.01 wt % to about 0.2 wt ) of the stabilizing agent.
  • Another aspect of the present invention provides a rechargeable battery comprising a cathode comprising a cathode active material comprising silver and a stabilizing agent; an anode comprising zinc; and an electrolyte, wherein the stabilizing agent comprises a powder having a mean particle diameter of about 250 nm or less (e.g., about 100 run or less), and the rechargeable battery provides at least about 12 Ah of aggregate battery capacity per gram of silver over a period of no more than about 1000 consecutive charge cycles.
  • the stabilizing agent comprises a powder having a mean particle diameter of about 250 nm or less (e.g., about 100 run or less)
  • the rechargeable battery provides at least about 12 Ah of aggregate battery capacity per gram of silver over a period of no more than about 1000 consecutive charge cycles.
  • the silver comprises Ag, AgO, Ag 2 0, Ag 2 0 3 , AgOH, Ag(OH)2, Ag(OH) 3 , AgOOH, AgONa, AgOK, AgOLi, AgORb, AgOONa, AgOOK, AgOOLi, AgOORb, AgCu02, AgFe02, AgMn02, Ag2CuMn04, any hydrate thereof, or any combination thereof.
  • the silver further comprises Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is doped with a first dopant comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is coated with a coating agent comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is coated with a coating agent comprising Pb.
  • the silver is coated with a coating agent comprising Pb, and the silver is doped with a first dopant comprising Ga.
  • the stabilizing agent comprises a powder comprising a p- type semiconductor, an n-type semiconductor, or any combination thereof.
  • the stabilizing agent comprises a powder comprising ZnO, SiO , Zr0 2 , Ti0 2 , AI2O3, MgO, SiC, ln 2 0 3 , H02O3, ZnTi0 3 , B 2 0 3 , L1AIO2, BaTi0 3 , LL Ca x Si04, Li4-xMg x Si0 4 , Bi 2 0 3 , Yb 2 0 3 , Mn0 2 , Ultramarine, or any combination thereof, wherein x is 1-4.
  • the stabilizing agent comprises a powder comprising ZnO.
  • the ZnO is doped with a second dopant comprising A1 2 0 3 , iron oxide, indium oxide, or any combination thereof.
  • the ZnO is doped with a second dopant comprising AhQj.
  • the stabilizing agent comprises a powder comprising Zr0 2 .
  • the stabilizing agent comprises a powder comprising Si0 2 .
  • the stabilizing agent comprises a powder, and the powder comprises a plurality of particles comprising S1O2, Zr0 2 , and ZnO.
  • the stabilizing agent comprises a powder comprising S1O2 particles, Zr0 2 particles, and ZnO particles.
  • the ZnO particles are doped with a second dopant comprising Al20 3 .
  • the ZnO particles comprise from about 1 wt % to about 10 wt % of AI2O 3 by weight of the ZnO particles.
  • the cathode active material comprises about 0.5 wt % or less (e.g., about 0.2 wt% or less) of the stabilizing agent.
  • the cathode active material comprises from about 0.01 wt % to about 0.3 wt % (e.g., from about 0.01 wt % to about 0.2 wt %) of the stabilizing agent
  • Another aspect of the present invention provides a method of producing a cathode comprising providing silver; providing a stabilizing agent comprising a powder having a mean particle diameter of no more than about 2S0 nm (e.g., about 100 nm or less); and associating the silver material with one or more particles of the stabilizing agent.
  • the silver comprises Ag, AgO, Ag20, Ag20 , AgOH, Ag(OH)2, Ag(OH) 3 , AgOOH, AgONa, AgOK, AgOLi, AgORb, AgOONa, AgOOK, AgOOLi, AgOORb, AgCuCh, AgFe02, AgMnCh, Ag2CuMn0 4 , any hydrate thereof, or any combination thereof.
  • the silver further comprises Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is doped with a first dopant comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is doped with a first dopant comprising Ga.
  • the silver is coated with a coating agent comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is coated with a coating agent comprising Pb.
  • the silver is coated with a coating agent comprising Pb, and the silver is doped with a first dopant comprising Ga.
  • the stabilizing agent comprises a powder comprising ZnO, S1O2, Zr0 2 , Ti0 2 , AI2O3, MgO, SiC, ⁇ 2 ⁇ 3 , Ho 2 0 3 , ZnTi0 3 , B2O3, L1AIO2, BaTiCb, Li 4 -,Ca x Si0 4 , LU-xMg x Si0 4 , Bi20 3 , Yb20 3 , MnCh, Ultramarine, or any combination thereof, wherein x is 1 - 4.
  • the stabilizing agent comprises a powder comprising ZnO.
  • the ZnO is doped with a second dopant comprising Al20 3 , iron oxide, indium oxide, or any combination thereof.
  • the ZnO is doped with a second dopant comprising A 0 3 .
  • the stabilizing agent comprises a powder comprising Z1O2.
  • the stabilizing agent comprises a powder comprising S1O2.
  • the stabilizing agent comprises a powder, and the powder comprises a plurality of particles comprising S1O2, Z1O2, and ZnO.
  • the stabilizing agent comprises a powder comprising Si02 particles, Z1O2 particles, and ZnO particles.
  • the ZnO particles are doped with a second dopant comprising A1 2 0 3 .
  • ZnO particles are doped with from about 1 wt% to about 10 wt% of a second dopant comprising AI2O3 by weight of the ZnO particles.
  • Some methods further comprise providing about 7 wt % or less (e.g., about 0.5 wt% or less) of the stabilizing agent. For example, providing from about 0.01 wt % to about 0.2 wt % of the stabilizing agent.
  • Another aspect of the present invention provides a method of improving the Coulombic efficiency of a silver cathode comprising adding a stabilizing agent to the silver cathode, wherein the stabilizing agent comprises a powder, and the powder has a mean particle diameter of no more than 100 nm.
  • the silver comprises Ag, AgO, Ag 2 0, Ag 2 0 3 , AgOH, Ag(OH) 2 , Ag(OH) 3 , AgOOH, AgONa, AgOK, AgOLi, AgORb, AgOONa, AgOOK, AgOOLi, AgOORb, AgCu02, AgFe0 2 , AgMn02, Ag 2 CuMn0 4 , any hydrate thereof, or any combination thereof.
  • the silver further comprises Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is doped with a first dopant comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is doped with a first dopant comprising Ga.
  • the silver is coated with a coating agent comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is coated with a coating agent comprising Pb.
  • the silver is coated with a coating agent comprising Pb, and the silver is doped with a first dopant comprising Ga.
  • the stabilizing agent comprises a powder comprising a p-type semiconductor, an n-type semiconductor, or any combination thereof.
  • the stabilizing agent comprises a powder comprising ZnO, S1O2, Z1O2, T1O2, AI2O3, MgO, SiC, ⁇ 2 0 3 , H02O3, ZnTi0 3 , B 2 0 3 , L1AIO2, BaTi0 3) Li4-xCa x Si0 4 , Li ⁇ -MgxSiO,*, Bi 2 0 3 , ⁇ 13 ⁇ 40 3 , ⁇ 2 , Ultramarine, or any combination thereof, wherein x is 1-4.
  • the stabilizing agent comprises a powder comprising ZnO.
  • the ZnO is doped with a second dopant comprising Al 2 0 3 , iron oxide, indium oxide, or any combination thereof.
  • the ZnO is doped with a second dopant comprising AI2O3.
  • the stabilizing agent comprises a powder comprising Zr0 2 .
  • the stabilizing agent comprises a powder comprising S1O2.
  • the stabilizing agent comprises a powder, and the powder comprises a plurality of particles comprising S1O2, Z1O2, and ZnO.
  • the stabilizing agent comprises a powder comprising Si0 2 particles, ⁇ 1 ⁇ 2 particles, and ZnO particles.
  • the ZnO particles are doped with a second dopant comprising AI2O3.
  • the ZnO particles comprise from about 1 wt% to about 10 wt of AI2O3 by weight of the ZnO particles.
  • Some methods further comprise adding about 7 wt % or less (e.g., about 0.5 wt or less) of the stabilizing agent by weight of the silver cathode. For example, adding from about 0.01 wt % to about 0.2 wt % of the stabilizing agent
  • the silver cathode further comprises a binder such as PTFE.
  • Figure 1 is a flow diagram that illustrates the steps of an exemplary method for producing cathode material according to one aspect of the present invention
  • Figure 2 is a graphical representation of the diffraction scanning calorimetry data recorded for Example Nos. 1 and 2;
  • Figure 3 is a graphical representation of the diffraction scanning calorimetry data recorded for Example Nos. 1, 3, and 4;
  • Figure 4 is a graphical representation of the TGA-DTA data of Example Nos. 1 and 2;
  • Figure 5 is an illustration of an electrochemical test cell that was used to test the electrical properties of exemplary cathode materials of the present invention
  • Figure 6 is a graphical representation of cell capacities as a function of charge cycles for test cells 1-4 that are formed from cathode materials described in Example Nos. I-
  • Figure 7 is a graphical representation of the ratio of the cell discharge to charge as a function of charge cycles for test cells 1-4 that are formed from cathode materials described in Example Nos. 1-4;
  • Figure 8 is a graphical representation of the voltage at the end of discharge as a function of charge cycles for test cells 1-4 that are formed from cathode materials described in Example Nos. 1-4;
  • Figure 9 is a graphical representation of the voltage at the end of charge as a function of charge cycles for test cells 1-4 that are formed from cathode materials described in Example Nos. 1-4;
  • Figure 10 is a graphical representation of cell capacities as a function of charge cycles for test cell 5 that is formed from cathode materials described in Example No. 5;
  • Figure 11 is a graphical representation of the voltage at the end of discharge as a function of charge cycles for test cell 5 that is formed from cathode materials described in Example No. 5;
  • Figure 12 is a graphical representation of cell capacities as a function of charge cycles for test cell 6 that is formed from cathode materials described in Example No! 6;
  • Figure 13 is a graphical representation of the voltage at the end of discharge as a function of charge cycles for test cell 6 that is formed from cathode materials described in Example No. 6;
  • Figurel4A is an SEM image of AgO cathode material of Example No. 1 prior to charge cycling;
  • Figure 14B is an SEM image of AgO cathode material of Example No. 8, prior to cycling;
  • Figure 15A is an SEM image of AgO cathode material of Example No. 1 after 5 charge cycles.
  • Figure 1 SB is an SEM image of AgO cathode material of Example No. 8 after 5 charge cycles.
  • the present invention provides cathodes, methods of making cathodes, and electrochemical cells (e.g., batteries) that have improved properties over traditional cathodes, methods, or electrochemical cells.
  • electrochemical cells e.g., batteries
  • the term “battery” encompasses electrical storage devices comprising one electrochemical cell (e.g., a button cell, a coin cell, or the like) or a plurality of electrochemical cells.
  • a “secondary battery” is rechargeable, whereas a “primary battery” is not rechargeable.
  • a battery anode is designated as the positive electrode during discharge, and as the negative electrode during charge.
  • the terms "silver” or “silver material” refer to any silver compound such as Ag, AgO, AgzO, Ag 2 0 3 , AgOH, Ag(OH) 2 , Ag(OH) 3 , AgOOH, AgONa, AgOK, AgOLi, AgORb, AgOONa, AgOO , AgOOLi, AgOORb, AgCuCh, AgFeO ⁇ AgMn0 2 , Ag 2 CuMn04, any hydrate thereof, or any combination thereof. Note that 'hydrates' of silver include hydroxides of silver.
  • the coordination sphere surrounding a silver atom is dynamic during charging and discharging of the cell wherein the silver serves as a cathode, or when the oxidation state of the silver atom is in a state of flux, it is intended that the term 'silver' or 'silver material' encompass any of these silver oxides and hydrates (e.g., hydroxides). Terms 'silver' or 'silver material' also includes any of the abovementioned species that are doped and/or coated with dopants and/or coatings that enhance one or more properties of the silver. Exemplary dopants and coatings are provided below.
  • silver or silver material includes a silver oxide further comprising a first row transition metal dopant or coating.
  • silver includes silver-copper-oxide, silver- iron-oxide, silver-manganese-oxide (e.g., AgMnOa), silver-chromium-oxide, silver- scandium-oxide, silver-cobalt-oxide, silver-titanium-oxide, silver-vanadium-oxide, hydrates thereof, or any combination thereof.
  • AgMnOa silver-manganese-oxide
  • silver-chromium-oxide silver- scandium-oxide
  • silver-cobalt-oxide silver-titanium-oxide
  • silver-vanadium-oxide hydrates thereof, or any combination thereof.
  • One generic formula for silver oxide is AgOv(OH) y (H 2 0) z , wherein v, y, and z are real numbers or zero, and at least one of v, y, or z is greater than zero.
  • a silver oxide may have a chemical formula of AgO, Ag 2 0 3 , or a combination thereof.
  • silver can comprise a bulk material or silver can comprise a powder having any suitable mean particle diameter.
  • iron oxide refers to any oxide or hydroxide of iron, e.g., FeO, Fe 2 0 3 , FeaOi, or any combination thereof.
  • indium oxide refers to any oxide or hydroxide of indium, e.g., In 2 0 3 .
  • alkaline battery refers to a primary battery or a secondary battery, wherein the primary or secondary battery comprises an alkaline electrolyte.
  • a "dopant” or “doping agent” refers to a chemical compound that is added to a substance in low concentrations in order to alter the optical/electrical properties of the semiconductor.
  • a dopant may be added to the powder active material of a cathode to improve its electronic properties (e.g., reduce its impedance and/or resistivity).
  • doping occurs when one or more atoms of a crystal lattice of a bulk material is substituted with one or more atoms of a dopant
  • an electrolyte refers to a substance that behaves as an electrically conductive medium.
  • the electrolyte facilitates the mobilization of electrons and cations in the cell.
  • Electrolytes include mixtures of materials such as aqueous solutions of alkaline agents. Some electrolytes also comprise additives such as buffers.
  • an electrolyte comprises a buffer comprising a borate or a phosphate.
  • Exemplary electrolytes include, without limitation, aqueous KOH, aqueous NaOH, or the liquid mixture of KOH in a polymer.
  • alkaline agent refers to a base or ionic salt of an alkali metal (e.g., an aqueous hydroxide of an alkali metal). Furthermore, an alkaline agent forms hydroxide ions when dissolved in water or other polar solvents.
  • alkaline electrolytes include without limitation LiOH, NaOH, KOH, CsOH, RbOH, or combinations thereof. Electrolytes can optionally include other salts to modify the total ionic strength of the electrolyte, for example KF or Ca(OH>2.
  • a “cycle” or “charge cycle” refers to a consecutive charge and discharge of a cell or a consecutive discharge and charge of a cell, either of which includes the duration between the consecutive charge and discharge or the duration between the consecutive discharge and charge.
  • a cell undergoes one cycle when, freshly prepared, it is discharged to about 100% of its DOD and re-charged to about 100% of its state of charge (SOC).
  • SOC state of charge
  • a freshly prepared cell undergoes 2 cycles when the cell is:
  • Cycle 1 discharged to about 100% of its DOD and re-charged to about 100% SOC; followed by
  • Cycle 2 a second discharge to about 100% of its DOD and re-charged to about 100% SOC.
  • PTFE corresponding initials
  • adjectives to distinguish polymers, solutions for preparing polymers, and polymer coatings. Use of these names and initials in no way implies the absence of other constituents.
  • adjectives also encompass substituted and co-poiymerized polymers.
  • a substituted polymer denotes one for which a substituent group, a methyl group, for example, replaces a hydrogen on the polymer backbone.
  • Ah refers to Ampere (Amp) Hour and is a scientific unit for the capacity of a battery or electrochemical cell.
  • a derivative unit, "mAh” represents a milliamp hour and is 1/1000 of an Ah.
  • maximum voltage or “rated voltage” refers to the maximum voltage an electrochemical cell can be charged without interfering with the cell's intended utility.
  • the maximum voltage is less than about 2.3 V, or about 2.0 V.
  • the maximum voltage is less than about 15.0 V (e.g., less than about 13.0 V, or about 12.6 V or less).
  • the maximum voltage for a battery can vary depending on the number of charge cycles constituting the battery's useful life, the shelf -life of the battery, the power demands of the battery, the configuration of the electrodes in the battery, and the amount of active materials used in the battery.
  • an “anode” is an electrode through which (positive) electric current flows into a polarized electrical device.
  • the anode is the negative electrode from which electrons flow during the discharging phase in the battery.
  • the anode is also the electrode that undergoes chemical oxidation during the discharging phase.
  • the anode is the electrode that undergoes chemical reduction during the cell's charging phase.
  • Anodes are formed from electrically conductive or semiconductive materials, e.g., metals, metal oxides, metal alloys, metal composites, semiconductors, or the like. Common anode materials include Si, Sn, Al, Ti, Mg, Fe, Bi, Zn, Sb, Ni, Pb, Li, Zr, Hg, Cd, Cu, LiC 6 , mischmetals, alloys thereof, oxides thereof, or composites thereof.
  • Anode materials such as zinc may even be sintered.
  • Anodes may have many configurations.
  • an anode may be configured from a conductive mesh or grid that is coated with one or more anode materials.
  • an anode may be a solid sheet or bar of anode material.
  • a "cathode” is an electrode from which (positive) electric current flows out of a polarized electrical device.
  • the cathode In a battery or galvanic cell, the cathode is the positive electrode into which electrons flow during the discharging phase in the battery.
  • the cathode is also the electrode that undergoes chemical reduction during the discharging phase.
  • the cathode is the electrode that undergoes chemical oxidation during the cell's charging phase.
  • Cathodes are formed from electrically conductive or semiconductive materials, e.g., metals, metal oxides, metal alloys, metal composites, semiconductors, or the like.
  • cathode materials include Ag, AgO, Ag 2 0 3 , Ag 2 0, HgO, Hg 2 0, CuO, CdO, NiOOH, ⁇ 3 ⁇ 40 4 , PbOa, LiFeP0 , Li 3 V 2 (P0 4 ) 3 , V 6 0, 3 , V 2 0 5 , Fe 3 0 4 , Fe 2 0 3 , Mn0 2 , L1C0O2, LiNiC ⁇ , LiMn 2 0 4 , or composites thereof.
  • Cathode materials such as Ag, AgO, Ag 2 0 3 may even be sintered.
  • Cathodes may also have many configurations.
  • a cathode may be configured from a conductive mesh that is coated with one or more cathode materials.
  • a cathode may be a solid sheet or bar of cathode material.
  • the term "Coulombic efficacy" refers to the number of Coulombs removed from a battery cell on discharge divided by the number of Coulombs that are added into the cell on charge.
  • electronic device is any device that is powered by electricity.
  • electronic device can include a portable computer, a portable music player, a cellular phone, a portable video player, or any device that combines the operational features thereof.
  • cycle life is the maximum number of times a secondary battery can be cycled while retaining a capacity useful for the battery's intended use (e.g., the number of times a cell may be cycled until the cell's 100% SOC, i.e., its actual capacity, is about 90% or less of its rated capacity (e.g., less than 85% of its rated capacity, about 90% of its rated capacity, or about 80% of its rated capacity).
  • 'cycle life' is the number of times a secondary battery or cell can be cycled until the cell's 100% SOC is at least about 60 percent of its rated capacity (e.g., at least about 70 percent of its rated capacity, at least about 80 percent of its rated capacity, at least 90 percent of its rated capacity, at least 95 percent of its rated capacity, about 90% of its rated capacity, or about 80% of its rated capacity).
  • M denotes molar concentration
  • a zinc-silver battery comprises an anode comprising zinc and a cathode comprising a silver powder (e.g., Ag20a). Nonetheless, more than one species is present at a battery electrode under most conditions.
  • a zinc electrode generally comprises zinc metal and zinc oxide (except when fully charged), and a silver powder electrode usually comprises AgO, AgzOj and/or Ag 2 0 and silver metal (except when fully discharged).
  • oxide applied to alkaline batteries and alkaline battery electrodes encompasses corresponding "hydroxide” species, which are typically present, at least under some conditions.
  • binder refers to a dry, bulk solid composed of a plurality of fine particles that may flow freely when shaken or tilted.
  • mean diameter or “mean particle diameter” refers to the diameter of a sphere that has the same volume/surface area ratio as a particle of interest.
  • the terms “substantially stable” or “substantially inert” refer to a compound or component that remains substantially chemically unchanged in the presence of an alkaline electrolyte (e.g., potassium hydroxide) and/or in the presence of an oxidizing agent (e.g., silver ions present in the cathode or dissolved in the electrolyte).
  • an alkaline electrolyte e.g., potassium hydroxide
  • an oxidizing agent e.g., silver ions present in the cathode or dissolved in the electrolyte
  • charge profile refers to a graph of an electrochemical cell's voltage or capacity with time.
  • a charge profile can be superimposed on other graphs such as those including data points such as charge cycles or the like.
  • resistivity refers to the internal resistance of a cathode in an electrochemical cell. This property is typically expressed in units of Ohms or micro-Ohms.
  • first and/or “second” do not refer to order or denote relative positions in space or time, but these terms are used to distinguish between two different elements or components.
  • a first separator does not necessarily proceed a second separator in time or space; however, the first separator is not the second separator and vice versa.
  • a first separator does not necessarily proceed a second separator in time or space; however, the first separator is not the second separator and vice versa.
  • a first separator does not necessarily proceed a second separator in time or space; however, the first separator is not the second separator and vice versa.
  • a second separator precedes a first separator in space or time.
  • nanometer and “nm” are used interchangeably and refer to a unit of measure equaling lxlO "9 meters.
  • analogous cathode refers to a cathode of a pair of cathodes wherein the cathodes of the pair are substantially identical to each other (e.g., use substantially the same amount of cathode materials (e.g., silver, binder, dopants, coatings, or any combination thereof); and/or using substantially the same methods of manufacturing) whose most significant difference is that one cathode of the pair is substantially free of stabilizing agent.
  • substantially identical to each other e.g., use substantially the same amount of cathode materials (e.g., silver, binder, dopants, coatings, or any combination thereof); and/or using substantially the same methods of manufacturing) whose most significant difference is that one cathode of the pair is substantially free of stabilizing agent.
  • Ultramarine refers to a blue pigment consisting primarily of a double silicate of aluminum and sodium with some sulfides or sulfates, and occurring in nature as a proximate component of lapis lazuli.
  • the pigment color code is P. Blue 29 77007.
  • Ultramarine is one of the most complex mineral pigments, a complex sulfur-containing sodio-silicate ( ag.ioAl6Si6024S2- ), essentially a mineralized limestone containing a blue cubic mineral called lazurite (the major component in lapis lazuli). Some chloride is often present in the crystal lattice as well.
  • the blue color of the pigment is due to the S 3" radical anion, which contains an unpaired electron.
  • 'Ultramarine' also refers to mixed aluminum silicates such as those prepared in a laboratory setting.
  • the term "cathode active material” refers to a composition that includes silver, as described above (e.g., doped silver, coated silver, silver that is doped or coated, or any combination thereof), and one or more stabilizing agents.
  • battery capacity or “capacity” refer to the mathematical product of a battery's discharge current and the time (in hours) during which the current is discharged.
  • aggregate capacity refers to the sum of a battery's capacities, i.e., the sum of the individual products of discharge current and the time during which the current is discharged, after being discharged to about 100 percent depth of discharge (e.g., more than 97.5 % depth of discharge, or more than 99 % depth of discharge) over a course of one or more charge cycles.
  • depth of discharge and “DOD” are used interchangeably to refer to the measure of how much energy has been withdrawn from a battery or cell, often expressed as a percentage of capacity, e.g., rated capacity. For example, a 100 Ah battery from which 30 Ah has been withdrawn has undergone a 30% depth of discharge (DOD).
  • DOD depth of discharge
  • state of charge and “SOC” and used interchangeably to refer to the available capacity remaining in a battery, expressed as a percentage of the cell or battery's rated capacity.
  • One aspect of the present invention provides a cathode for use in a rechargeable battery comprising a cathode active material comprising a stabilizing agent comprising a powder having a mean particle diameter of about 250 nm or less (e.g., about 100 nm or less); and silver, wherein the stabilizing agent is present in an amount sufficient to impart the cathode with a Coulombic efficiency of greater than about 90 % (e.g., greater than about 95 % or greater than about 98 %).
  • the cathode active material comprises silver
  • the silver comprises Ag, AgO, A&O, Ag 2 0 3 , AgOH, Ag(OH)2, Ag(OH) 3 , AgOOH, AgONa, AgOK, AgOLi, AgORb, AgOONa, AgOOK, AgOOLi, AgOORb, AgCuC , AgFe0 2 , AgMnCh, AgzCuMnO ⁇ , any hydrate thereof, or any combination thereof.
  • the silver further comprises Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is doped with a first dopant comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is doped with a first dopant comprising Ga.
  • silver is coated with a coating agent comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is coated with a coating agent comprising Pb.
  • the silver is doped with a first dopant comprising Ga, and the silver is coated with a coating agent comprising Pb.
  • the silver of the cathode active material comprises a powder or a bulk material (e.g., a silver foil, silver pellets, a combination thereof, or the like).
  • the stabilizing agent comprises a powder comprising a p- type semiconductor, an n-type semiconductor, or any combination thereof.
  • the stabilizing agent comprises a powder comprising ZnO, S1O2, Z1O2, T1O2, AI2O3, MgO, SiC, ⁇ 2 0 3 , H02O3, ZnTi0 3> B 2 0 3 , LLAIO2, BaTi0 3 , LU-xCaxSiO,,, LU-iMgxSiO,, Bi 2 0 3 , ⁇ 13 ⁇ 40 3 , ⁇ 2, Ultramarine, or any combination thereof, wherein x is 1-4.
  • the stabilizing agent comprises a powder comprising ZnO.
  • the ZnO is doped with a second dopant comprising Al20 3 , iron oxide, indium oxide, or any combination thereof.
  • the ZnO is doped with a second dopant comprising AU0 3 .
  • the stabilizing agent comprises a powder comprising Zr02.
  • the stabilizing agent comprises a powder comprising Si02.
  • the Si0 2 is doped with A1 2 0 3 (e.g., from about 1 wt % to about 1- wt% of Al20 3 ).
  • the stabilizing agent comprises a powder, and the powder comprises a plurality of particles comprising S1O2, Z1O2, and ZnO. In other examples, the stabilizing agent comprises a powder comprising SK3 ⁇ 4 particles, Z1O2 particles, and ZnO particles. In some instances, the ZnO particles are doped with a second dopant comprising A1 2 0 3 . In other instances, the ZnO particles comprise from about 1 wt % to about 10 wt % of Al20 3 by weight of the ZnO particles.
  • the cathode active material comprises about 7 wt % or less (e.g., about 5 wt % or less, about 2 wr% or less, about 1 wt % or less, about 0.5 wt % or less, or about 0.2 wt% or less) of the stabilizing agent.
  • the cathode active material comprises from about 0.005 wt % to about 0.5 wt % (e.g., from about 0.01 wt% to about 0.3 wt% or from about 0.0 i wt % to about 0.2 wt %) of the stabilizing agent.
  • the cathode further comprises a binder.
  • Binders suited for use in cathodes of the present invention may comprise any material that can sequester silver powder particles and are substantially inert in the presence of strong alkaline solutions and silver compounds (e.g., AgO or the like).
  • the cathode comprises a binder comprising PTFE.
  • the binder comprises PVDF.
  • the cathode active material comprises a powder that comprises a plurality of particles comprising silver and a plurality of particles comprising a stabilizing agent, wherein at least one particle of silver is associated with at least one particle of a stabilizing agent, the plurality of particles of the stabilizing agent have a mean particle diameter of about 250 run or less (e.g., about 100 nm or less), and the stabilizing agent is present in an amount sufficient to impart the cathode with a Coulombic efficacy of greater than about 90 % (e.g., greater than about 95 % or greater than about 98 %).
  • Another aspect of the present invention provides a cathode for use in a rechargeable battery comprising a cathode active material comprising a stabilizing agent comprising a powder having a mean particle diameter of 100 nm or less; and silver, wherein the stabilizing agent is present in an amount sufficient to impart the cathode with a Coulombic efficiency that is at least 10 % higher than an analogous cathode whose only significant difference is the absence of a stabilizing agent.
  • a cathode for use in a rechargeable battery comprising a cathode material
  • the cathode material comprises a powder.
  • the powder comprises a plurality of particles comprising silver and a plurality of particles having a mean particle diameter of about 250 nm or less (e.g., about 100 nm or less) comprising a stabilizing agent, wherein at least one particle of silver is associated with at least one particle of a stabilizing agent, wherein the stabilizing agent is present in an amount sufficient to impart the cathode with a Coulombic efficiency that is at least 10 % higher than an analogous cathode whose only significant difference is the absence of a stabilizing agent.
  • Silver is associated with the at least one particle of stabilizing agent when that particle of stabilizing agent is completely embedded in silver, partially embedded in the silver, contacting a surface of an silver particle, or almost contacting a surface of a silver particle (e.g., within 10 nm of an AgO surface), whether the silver comprises a powder or a bulk material.
  • Cathodes of the present invention can include any suitable stabilizing agent so long as the stabilizing agent is in the form of a powder that comprises particles having a mean diameter of about 250 nm or less (e.g., about 100 nm or less).
  • the stabilizing agent may comprises a p-type semiconductor, an n-type semiconductor, or a combination thereof.
  • the stabilizing agent comprises a plurality of particles comprising ZnO, S1O2, ⁇ 1 ⁇ 2, Ti0 2 , A1 2 0 3 , MgO, SiC, ⁇ ⁇ 2 0 3 , H02O3, ZnTi0 3 , B2O3, L1AIO2, BaTiCh, LU-xCaxSiO Li4- x Mg A Si0 4 , B12O3, YD2O3, MnOi, Ultramarine, or any combination thereof.
  • the stabilizing agent may be present in any suitable amount.
  • the stabilizing agent is present in an amount of about 7 wt % or less (e.g., about 5 wt % or less, about 1.5 wt% or less, or about 0.5 wt % or less (e.g., about 0.45 wt % or less, about 0.30 wt % or less, about 0.20 wt % or less, or about 0.15 wt % or less)) by weight of the cathode material. In other instances, the stabilizing agent is present in an amount of from about 0.01 wt % to about 0.2 wt % by weight of the cathode material.
  • the particles that comprise the stabilizing agent may be further modified to improve one or more of their chemical, electrical, or physical properties.
  • the stabilizing agent particles may be doped and/or coated with any suitable additive that does not substantially impair the ability of the stabilizing agent to associate with Silver.
  • the stabilizing agent can comprise any suitable combination of n-type and/or p-type
  • the stabilizing agent comprises ZnO.
  • the stabilizing agent comprises ZnO that is doped with AI2O3.
  • the stabilizing agent comprises Z1O2.
  • the stabilizing agent comprises Si0 2 .
  • the stabilizing agent comprises a plurality of particles and each of the particles comprises S1O2, Z1O2, or ZnO (e.g., ZnO that is doped with AI2O3).
  • the stabilizing agent comprises a plurality of particles comprising a combination of S1O2 particles, ⁇ particles, and ZnO particles.
  • the ZnO particles are doped with AI2O 3 .
  • the ZnO particles are doped with from about 1 wt% to about 10 wt% of AI2O3 by weight of the doped ZnO particles.
  • the S1O2 is doped with Al20 3 (e.g., from about 1 wt % to about 1- wt of AI2O3).
  • cathodes of the present invention can include silver that is doped or coated.
  • the silver is doped with a doping agent comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is coated with a coating agent comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • Cathodes of the present invention can further include optional additives such as a colorant, a current collector, or the like.
  • a cathode material may comprises a binder such as PTFE.
  • Another aspect of the present invention provides a cathode for use in a rechargeable battery comprising a cathode material, and the cathode material comprises a powder.
  • the powder comprises particles comprising silver that is associated with a first stabilizing agent (e.g., ZnO or ZnO doped with AI2O3), particles comprising silver that is associated with a second stabilizing agent (e.g., ZrCh), and particles comprising silver that is associated with a third stabilizing agent (e.g., S1O2).
  • a first stabilizing agent e.g., ZnO or ZnO doped with AI2O3
  • a second stabilizing agent e.g., ZrCh
  • S1O2O2O2O2O2O2 e.g., S1O2
  • a rechargeable battery comprising a cathode comprising a cathode active material comprising silver and a stabilizing agent; an anode comprising zinc; and an electrolyte
  • the stabilizing agent comprises a powder having a mean particle diameter of about 250 nm or less (e.g., about 100 nm or less)
  • the silver associates with one or more particles of the stabilizing agent
  • the stabilizing agent is present in an amount sufficient to impart the cathode with a Coulombic efficiency of greater than about 90 % (e.g., greater than about 95 % or greater than about 98 %).
  • the silver comprises Ag, AgO, Ag20, Ag203, AgOH, Ag(OH) 2 , Ag(OH) 3 , AgOOH, AgONa, AgO , AgOLi, AgORb, AgOONa, AgOOK, AgOOLi, AgOORb, AgCu ⁇ 3 ⁇ 4, AgFe02, AgMn(3 ⁇ 4, Ag2CuMn0 4 , any hydrate thereof, or any combination thereof.
  • the silver further comprises Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is doped with a first dopant comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is coated with a coating agent comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is coated with a coating agent comprising Pb.
  • the silver is coated with a coating agent comprising Pb, and the silver is doped with a first dopant comprising Ga.
  • the stabilizing agent comprises a powder comprising a p- type semiconductor, an n-type semiconductor, or any combination thereof.
  • the stabilizing agent comprises a powder comprising ZnO, S1O2, Z1O2, T1O2, AI2O3, MgO, SiC, ⁇ 2 0 3 , H02O3, ZnTi0 3 , B 2 0 3 , L1AIO2, BaTi0 3 , Li4-xCa x Si0 4 , Lu-xMg x Si0 4 , Bi 2 0 3( ⁇ 2 ⁇ 3 , ⁇ 2 , Ultramarine, or any combination thereof, wherein x is 1-4.
  • the stabilizing agent comprises a powder comprising ZnO.
  • the ZnO is doped with a second dopant comprising A1 2 0 3 , iron oxide, indium oxide, or any combination thereof.
  • the ZnO is doped with a second dopant comprising A1 2 0 .
  • the stabilizing agent comprises a powder comprising Z1O2.
  • the stabilizing agent comprises a powder comprising Si0 2 .
  • the S1O2 is doped with A Oj ie.g., from about 1 wt % to about 1- wt% of A1 2 0 3 ).
  • the stabilizing agent comprises a powder, and the powder comprises a plurality of particles comprising S1O2, ⁇ 1 ⁇ 2, and ZnO.
  • the stabilizing agent comprises a powder comprising Si0 2 particles, Z1O2 particles, and ZnO particles.
  • the ZnO particles are doped with a second dopant comprising ⁇ 2 ⁇ 3 .
  • the ZnO particles comprise from about 1 wt to about 10 wt% of AI2O3 by weight of the ZnO particles.
  • the cathode active material comprises about 7 wt % or less (e.g., about 0.5 wt or less or about 0.2 wt% or less) of the stabilizing agent.
  • the cathode active material comprises from about 0.01 wt % to about 0.2 wt % of the stabilizing agent.
  • Another aspect of the present invention provides a rechargeable battery comprising a cathode comprising a cathode material comprising a powder; an anode comprising zinc; and an electrolyte, wherein the powder comprises particles of silver and particles of stabilizing agent having a mean particle diameter of about 250 nm or less (e.g., about 100 nm or less), at least one particle of silver is associated with at least one particle of stabilizing agent, and the stabilizing agent is present in an amount sufficient to impart the cathode with an activity of greater than about 90 % (e.g., greater than about 95 % or greater than about 98%).
  • the powder comprises particles of silver and particles of stabilizing agent having a mean particle diameter of about 250 nm or less (e.g., about 100 nm or less)
  • at least one particle of silver is associated with at least one particle of stabilizing agent
  • the stabilizing agent is present in an amount sufficient to impart the cathode with an activity of greater than about 90 % (e.g.,
  • an electrochemical cell comprising a cathode comprising a cathode material comprising a powder, wherein the powder comprises a plurality of particles comprising silver that are associated with at least one particle of a stabilizing agent, and the stabilizing agent comprises a plurality of particles having a mean particle diameter of about 250 nm or less (e.g., about 100 nm or less); an anode comprising Zn; and an electrolyte, wherein the cathode of the electrochemical cell has sufficient stabilizing agent such that the cell retains a substantially constant capacity after more than about 70 charge cycles.
  • the rechargeable battery comprising a cathode comprising a cathode active material comprising silver and a stabilizing agent; an anode comprising zinc; and an electrolyte
  • the stabilizing agent comprises a powder having a mean particle diameter of about 250 nm or less
  • the rechargeable battery provides a battery capacity of at least about 140 mAh/g of silver per discharge for a period of at least about 100 consecutive charge cycles.
  • the battery provides a battery capacity of at least about 140 mAh/g of silver per discharge for a period of at least about 150 consecutive charge cycles. In other embodiments, the battery provides a battery capacity of more than about 140 mAh g of silver per discharge for a period of at least about 100 consecutive charge cycles. In some embodiments, the battery provides at least about 14 Ah/g of silver aggregate capacity over a period of no more than about 1000 consecutive charge cycles. And, in other embodiments, the battery provides at least about 200 raAh/g of silver per discharge for a period of at least about 150 (e.g., about 175 or more) consecutive charge cycles.
  • the rechargeable battery comprising a cathode comprising a cathode active material comprising silver and a stabilizing agent; an anode comprising zinc; and an electrolyte
  • the stabilizing agent comprises a powder having a mean particle diameter of about 250 nm or less (e.g., about 100 nm or less), and the rechargeable battery provides at least about 12 Ah of aggregate battery capacity per gram of silver over a period of no more than about 1000 consecutive charge cycles.
  • the rechargeable battery provides a battery capacity of at least about 140 mAh per gram of silver per discharge for a period of at least about 150 consecutive charge cycles.
  • the rechargeable battery provides a battery capacity of more than about 140 mAh per gram of silver per discharge for a period of at least about 100 consecutive charge cycles.
  • Another aspect of the present invention provides a rechargeable battery comprising a cathode comprising a cathode active material comprising silver and a stabilizing agent; an anode comprising zinc; and an electrolyte, wherein the stabilizing agent comprises a powder having a mean particle diameter of about 250 nm or less (e.g., about 100 nm or less), and the rechargeable battery provides an aggregate capacity of at least about 12 Ah per gram of silver over a period of no more than about 1000 consecutive charge cycles.
  • the stabilizing agent comprises a powder having a mean particle diameter of about 250 nm or less (e.g., about 100 nm or less)
  • the rechargeable battery provides an aggregate capacity of at least about 12 Ah per gram of silver over a period of no more than about 1000 consecutive charge cycles.
  • cathodes and cathode materials described above are suitable for use in a rechargeable battery of the present invention.
  • rechargeable batteries of the present invention may comprise any suitable electrolyte.
  • the electrolyte comprises an alkaline agent having any suitable concentration.
  • the alkaline agent comprises LiOH, NaOH, KOH, CsOH, RbOH, or any combination thereof.
  • the alkaline agent comprises a combination of NaOH and KOH.
  • the present invention also provides methods of producing a cathode described above.
  • the method of producing a cathode comprises providing silver; providing a stabilizing agent comprising a powder having a mean particle diameter of no more than about 250 nm (e.g., no more than about 100 nm); and associating the silver material with one or more particles of the stabilizing agent.
  • the silver comprises Ag, AgO, Ag 2 ⁇ ->, Ag 2 0 3 , AgOH, AgiOH ⁇ , Ag(OH) 3 , AgOOH, AgONa, AgOK, AgOLi, AgORb, AgOONa, AgOOK, AgOOLi, AgOORb, AgCu0 2 , AgFe0 2 , AgMnOi, Ag 2 CuMnO,», any hydrate thereof, or any combination thereof.
  • the silver further comprises Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is doped with a first dopant comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is doped with a first dopant comprising Ga.
  • the silver is coated with a coating agent comprising Pb, B, Al, Ga, Zn, Ni, Pd, In, Fe, or any combination thereof.
  • the silver is coated with a coating agent comprising Pb.
  • the silver is coated with a coating agent comprising Pb, and the silver is doped with a first dopant comprising Ga.
  • the stabilizing agent comprises a powder comprising ZnO, SiC , Zr0 2 , T1O2, AI2O3, MgO, SiC, ln 2 0 3 , H02O3, ZnTi0 3 , B 2 0 3 , LiA10 2 , BaTi0 3 , Li4-xCa x Si0 4 , Li4. x MgxSi04, B12O3, Yb 2 ⁇ 3 ⁇ 4, ⁇ 2 , Ultramarine, or any combination thereof, wherein x is 1- 4.
  • the stabilizing agent comprises a powder comprising ZnO.
  • the ZnO is doped with a second dopant comprising ⁇ 2 ⁇ 3 , iron oxide, indium oxide, or any combination thereof.
  • the ZnO is doped with a second dopant comprising A1 2 0 3 .
  • the stabilizing agent comprises a powder comprising Zr0 2 -
  • the stabilizing agent comprises a powder comprising S1O2.
  • the Si0 2 is doped with Al20 3 (e.g., from about 1 wt % to about 1 - wt% of AJ2O3).
  • the stabilizing agent comprises a powder, and the powder comprises a plurality of particles comprising Si0 2 , ZrO?, and ZnO.
  • the stabilizing agent comprises a powder comprising Si0 2 particles, Z1O2 particles, and ZnO particles.
  • the ZnO particles are doped with a second dopant comprising AI 2 O 3 .
  • ZnO particles are doped with from about 1 wt% to about 10 wt% of a second dopant comprising A 0 3 by weight of the ZnO particles.
  • Some methods further comprise providing about 7 wt % or less (e.g., about 0.5 wt% or less) of the stabilizing agent. For example, providing from about 0.01 wt % to about 0.3 wt % (e.g., from about 0.01 wt % to about 0.2 wt %) of the stabilizing agent.
  • Another aspect of the present invention provides a method of improving the Coulombic efficiency of a silver cathode comprising adding a stabilizing agent to the silver cathode, wherein the stabilizing agent comprises a powder, and the powder has a mean particle diameter of no more than about 250 run (e.g., no more than about 100 nm).
  • Some methods further comprise adding about 7 wt % or less of the stabilizing agent by weight of the silver cathode. For example, adding from about 0.01 wt % to about 0.2 wt % of the stabilizing agent.
  • the silver cathode further comprises a binder such as PTFE.
  • Materials used for the preparation of cathodes of the present invention can, in many cases, include substitutions.
  • a KOH alkaline solution can be substituted with NaOH, LiOH, CsOH, combinations thereof, or the like.
  • Other substitutions are also possible.
  • gelatin may be replaced by one or more alternative surfactants.
  • nanopowders comprising stabilizing agents may be used interchangeably or in any suitable combination.
  • Silver nitrate A.C.S. grade, DFG
  • Potassium hydroxide solution 40% KOH solution, prepared from KOH pellets,
  • Zinc oxide doped with 6% Al, nanopowder, ⁇ 50nm (BET), >97%, Sigma-Aldrich
  • Zirconium(IV) oxide nanopowder, ⁇ 100 nm particle size (BET), Sigma-Aldrich -
  • Silica nanopowder, ⁇ 5nm, Nyacol Nano Technologies Inc.
  • a 2000 ml beaker was placed into a hot water bath and an overhead stirring propeller was installed. 116.7 g of AgN0 3 and 1000 g of DI water were added to the reaction container and stirred at 400rpm. 0.1 lg gelatin was added. The flask was heated to 55 °C.
  • Example 2 Exemplary Cathode Material Including a ZnO-Al 2 0 3 Stabilizing Agent
  • a 2000 ml beaker was placed into a hot water bath and an overhead stirring propeller was installed.
  • 1 16.7 g of AgN0 3 and 1000 g of DI water were added to the reaction container and stirred at a stir speed of 400 rpm.
  • 12 mg ZnO-AhOs was dispersed in 100 g DI water then added.
  • 0.11 g of gelatin was added, and the flask was heated to 55 °C.
  • Example 3 Exemplary Cathode Material Including a Si0 2 Stabilizing Agent
  • a 2000 ml beaker was placed into a hot water bath and an overhead stirring propeller was installed.
  • 1 16.7 g of AgN0 3 and 1000 g of DI water were added to the reaction container and stirred using a stir speed of 400 rpm.
  • 9 mg of silica was dispersed in 20 g of DI water then added.
  • 0.1 lg of gelatin was added. The flask was heated to 55 °C.
  • Example 4 Exemplary Cathode Material Including a Zr0 2 Stabilizing Agent
  • a 2000 ml beaker was placed into a hot water bath and an overhead stirring propeller was installed. 116.7 g of AgNOj and 1000 g of DI water were added to the reaction container and stirred using a stir speed of 400 rpm. 95mg zirconium (IV) oxide was dispersed in 100 g of DI water then added. 0.11 g gelatin was added. The flask was heated to 55 °C.
  • Example 5 Exemplary Cathode Material Including a Stabilizing Agent Formulated From Si0 2 , Zr0 2 , and ZnO doped with A1 2 0 3 .
  • a 4 L beaker was placed into a hot water bath and an overhead stirring propeller was installed. 233.4 g of AgN03 and 1200 g of DI water were added to the reaction container and stirred using a stir speed of 450 rpm. 0.2 g of gelatin was added. 26 mg of silica was dispersed in 50 g of DI water, 48 mg ZnO-Al 2 0 3 , and 240 mg of zirconium (IV) oxide (50nm, Alfa-Aesar) were dispersed in 58 g of DI water then added to the beaker. The beaker was heated to 55 °C.
  • Example 6 Exemplary Cathode Material Including a Gallium Doped, Lead Coated Silver Material and Stabilizing Agent Formulated From Si0 2 , Zr0 2 , and ZnO doped with AI2O 3 .
  • a 4 L beaker was placed into a hot water bath and an overhead stirring propeller was installed. 233.4 g of AgN0 3 and 1200 g of DI water were added to the reaction container and stirred at 450 rpm. 0.15 g of gelatin and 1.53 g gallium hydroxide were added. 32 mg silica was dispersed in 58 g water, 48 mg ZnO-Ab0 3 and 240 mg zirconium (IV) oxide (50nm, Alfa-Aesar) were dispersed in 61 g DI water then added. The beaker was heated to 55 °C.
  • This process generated about 170 g of Ga doped AgO.
  • Example 7 Exemplary Cathode Material Including AgCuO and Stabilizing Agent Formulated From S1O 2 and Zr0 2 .
  • a 2 L beaker was placed into a hot water bath and an overhead stirring propeller was installed.
  • 233 g of KOH solution (1.4g ml) was mixed with 233 g of DI water to produce a diluted KOH solution, which was stirred at 400 rpm.
  • the beaker was heated to 55 °C.
  • the above AgNO3 ⁇ 4 solution was added.
  • 173.6 g of potassium persulfate was added at 65 °C. After the addition of the potassium persulfate, the reaction flask was maintained at 65 °C for 30 min.
  • Example 8 Exemplary Cathode Material Including Physical Mixture of Stabilized Silver Oxide Formulated From Particles of AgO-SiC , AgO-Zr0 2 , and AgO- ZnO-AJ 2 0 3 .
  • the exemplary cathode material of Example No. 8 was prepared by physically mixing 25 g of each cathode material prepared as described above in Example Nos. 2, 3, and 4.
  • Example 9 Additional Exemplary Cathode Materials.
  • Table 1 Summary of formulations of exemplary cathodes of the present invention.
  • Formulations of several exemplary cathodes of the present invention are characterized below in Table 2, along with an AgO cathode that is provided for purposes of comparison.
  • Table 2 Summary of formulations of exemplary cathodes of the present invention.
  • the activity of the exemplary cathode materials described above was measured by titration. Material was crushed and or grinded with a spatula. If the sample was not completely dry, it was dried in a vacuum oven at 60 °C overnight. 0.100 g of sample was added directly into clean 125 ml flask, and weight was recorded accurately to at least the third decimal place. 10 ml of acetate buffer and 5 ml KI solution (59 %) was added to the flask. The flask was swirled to disperse particles. The flask was covered by putting an inverted small plastic cup over its top, and the covered flask was sonicated for 2 hours. 20 ml DI water was added to the flask.
  • the particle size of the product was analyzed using a Horiba laser diffractometer (model no. LA-930). Diameters on several population distributions (e.g., 5%, 10%, 20%, etc.) were recorded and are provided below in Table 2.
  • the resistivity of the cathode material was determined using the following method: 3 grams of sample cathode material was loaded into a press having a 3.88 cm 2 area. A force of from 10 to 40 metric tons was applied to the sample cathode material, and resistance was recorded at every 5 metric ton increment between 10 metric tons and 40 metric tons. Note that the resistivity of the sample is the value at infinite force.
  • the resistivities of samples are provided in Table 3, below.
  • Table 3 Characterization of several exemplary cathode materials.
  • Example 2 In Example 2, only 1.65 g of material was used for resistivity testing.
  • DSC Differential scanning calorimetry
  • TGA thermo gravimetric analysis
  • the initial exothermal peak is about same for samples with and without a stabilizing agent.
  • the samples having a stabilizing agent show slightly lower decomposition temperatures than samples using the cathode material of Example No. 1 , where no stabilizing agent is present, according to TGA-DTA data. The results indicate that these stabilized AgO cathode material samples, described in Example Nos. 2-5 above, were thermally stable.
  • Test cells were constructed for evaluation of the electrical properties of the exemplary cathode materials described in Example Nos. 1-6, above.
  • Figure 5 schematically illustrates the arrangement order of elements used in the silver-zinc test cells.
  • the electrolyte of aqueous alkaline is used for purpose of offering OH " during charge and discharge process.
  • Example Nos. 1-4 were incorporated into prismatic test cells having 2.0 Ah capacities, and the cathode materials described in Example Nos. 5 and 6 were incorporated into a prismatic test cell having a 3.0 Ah capacity.
  • the anodes of these test cells 1-5 were formed using 3.6 g zinc, with additives of zinc oxide (13 wt %) and B12O3 (03 wt %), and 5 wt% PTFE as a binder.
  • the anodes were configured into 43 mm x 31 mm rectangles that were pressed at 2 tons.
  • the rectangles along with 32 wt % KOH and NaOH (0.1 g) mixed electrolyte (80:20) with additives of In/brass (0.1 wt %) were wrapped in Solupor® (commercially available from Lydall, Inc. of Rochester, NH) and incorporated into the test cells as depicted in Figure 5.
  • Test cathodes were formed from cathode material including 3 wt% PTFE binder.
  • the cathode material was formed into 43 mm x 31 mm rectangles, pressed at 5.5T, and, along with 32% KOH and NaOH (0.2 g) mixed electrolyte (80:20) with additives of Pb (0.4 wt %), was wrapped in SL6-8 material commercially available from the Shilong Company.
  • test cells also included 2 distinct cellophane films, commercially available from Innovia Films, located between the wrapped electrodes that were soaked and filled with 32% KOH and NaOH mixed electrolyte. Table 4 describes the test cells.
  • Table 4 Test cells for measuring the electrical properties of cathode materials of novel cathode materials.
  • That cathode pouch material designated with the "T2" reference number is formed from a 3-layered co-extruded material.
  • the first layer i.e., the layer facing the cathode is a mixture of polystyrene sulfonic acid (PSS).and polyacrylic acid (PAA) (35 wt% PAA vs. PSS).
  • the second layer is a filled polyvinyl alcohol
  • the third layer is an unfilled polyvinyl alcohol. Structurally, the second layer is interposed between the first and third layers.
  • the second cathode layer is formulated from about ⁇ 10 wt% PVA and Z1O2 powder (-35 wt% Z1O2 vs. PVA).
  • the third layer was formulated from a 10 wt% PVA stock solution. The film was co-extruded and dried at low dryer temperatures. Each of the three layer is - 10 microns thick.
  • the "SL6-8” is an 8 micron thick film, that is commercially available from the Shilong Company.
  • T e cycle life of test cells having cathodes comprising a stabilizing agent was determined by repeatedly charging and discharging the test cell to evaluate the reduction of battery capacity as a function of charge cycles. It is noted that the period of time between a discharge and a charge in two consecutive charge cycles was less than 10 minutes.
  • a typical charge-discharged cycling procedure is as follows:
  • the battery is charged with a constant current until the battery terminal voltage reached 2.03 volts or more and then the voltage is held fixed at 2.03 volts until the desired charge capacity of the cell is reached.
  • the initial charge current is chosen to charge the battery in 5 hours. After charge the battery is allowed to rest for 10 to 30 minutes.
  • the battery is then discharged at a constant current until the battery voltage reached 1.2 volts or until 5 hours total discharge time is reached. The current is chosen to completely discharge the battery in 5 hours. After discharge the cell is allowed to rest from 10 to 30 minutes.
  • test cells having cathodes with a stabilizing agent have more desirable discharge coefficients, voltages at end of discharge, voltages at end of charge during cycling, at least in their early stages (e.g., about 160 charge cycles), and material properties, i.e., the silver particles in an exemplary cathode material comprising a stabilizing agent shows decreased aggregation after cycling than a cathode material lacking a stabilizing agent.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

Cette invention concerne des cathodes, leurs procédés de fabrication et des cellules électrochimiques (telles que des batteries) utilisant ces cathodes et possédant des propriétés améliorées par rapport à des cathodes, procédés ou cellules électrochimiques classiques. Les cathodes comprennent une matière cathodique active comprenant : un agent de stabilisation qui comprend une poudre ayant une granulométrie de 250 nm ou moins; et de l'argent.
PCT/US2010/055204 2009-11-03 2010-11-03 Nouvelles électrodes et batteries rechargeables WO2011056813A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP10776246.0A EP2497138B1 (fr) 2009-11-03 2010-11-03 Nouvelles électrodes et batteries rechargeables
CA2779090A CA2779090A1 (fr) 2009-11-03 2010-11-03 Nouvelles electrodes et batteries rechargeables
US13/504,986 US9184444B2 (en) 2009-11-03 2010-11-03 Electrodes and rechargeable batteries
JP2012537205A JP5806675B2 (ja) 2009-11-03 2010-11-03 新規の電極および再充電可能バッテリ

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US25757609P 2009-11-03 2009-11-03
US61/257,576 2009-11-03
US29588210P 2010-01-18 2010-01-18
US61/295,882 2010-01-18

Publications (1)

Publication Number Publication Date
WO2011056813A1 true WO2011056813A1 (fr) 2011-05-12

Family

ID=43608733

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2010/055204 WO2011056813A1 (fr) 2009-11-03 2010-11-03 Nouvelles électrodes et batteries rechargeables

Country Status (6)

Country Link
US (1) US9184444B2 (fr)
EP (1) EP2497138B1 (fr)
JP (1) JP5806675B2 (fr)
CA (1) CA2779090A1 (fr)
TW (1) TWI509867B (fr)
WO (1) WO2011056813A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130216901A1 (en) * 2010-09-24 2013-08-22 Zpower, Llc Cathode
CN103545535A (zh) * 2012-07-11 2014-01-29 丰田自动车株式会社 用于金属-空气电池的空气电极和金属-空气电池
WO2014052533A1 (fr) * 2012-09-27 2014-04-03 Zpower, Llc Cathode
US8936775B2 (en) 2008-10-29 2015-01-20 Zpower, Llc Cathode active material (higher oxides of silver)
US9184440B2 (en) 2010-11-03 2015-11-10 Zpower, Llc Electrodes and rechargeable batteries
US9209454B2 (en) 2009-03-27 2015-12-08 Zpower, Llc Cathode

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10177384B2 (en) * 2011-01-13 2019-01-08 Samsung Sdi Co., Ltd. Positive active material for rechargeable lithium battery, method of manufacturing the same and rechargeable lithium battery using the same
KR101746188B1 (ko) 2014-09-02 2017-06-12 울산과학기술원 이차 전지용 전극 합제 첨가제, 이의 제조 방법, 이를 포함하는 이차 전지용 전극 및 이차 전지
JP6747793B2 (ja) * 2015-09-16 2020-08-26 マクセルホールディングス株式会社 アルカリ二次電池
TWI608648B (zh) 2016-04-28 2017-12-11 國立交通大學 複合電極材料及其製造方法
EP3742531B1 (fr) 2018-01-18 2024-02-28 Maxell, Ltd. Pile alcaline secondaire et méthode de chargement de ladite pile alcaline
CN108847479B (zh) * 2018-06-20 2020-06-05 江苏海明斯新材料科技有限公司 一种锂电池正极材料用多孔层状化学结构改性硅酸镁锂的制备方法
CN108847355B (zh) * 2018-06-20 2019-11-26 江苏海明斯新材料科技有限公司 一种硅酸镁锂改性二氧化锰基超级电容器电极材料的制备方法
US10448137B1 (en) 2018-06-21 2019-10-15 Bose Corporation Dual zone discharge of rechargeable batteries
JP7121585B2 (ja) * 2018-08-22 2022-08-18 マクセル株式会社 アルカリ電池

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4167609A (en) * 1978-03-30 1979-09-11 Union Carbide Corporation Zinc oxide additive for divalent silver oxide electrodes
JPS60189164A (ja) * 1984-03-06 1985-09-26 Matsushita Electric Ind Co Ltd 酸化銀電池
US20030207173A1 (en) * 2002-05-06 2003-11-06 Francis Wang Alkaline cell with improved cathode
WO2008004105A1 (fr) * 2006-07-05 2008-01-10 S.C.P.S. Société de Conseil et de Prospective Scientifique S.A. Nouvelle électrode positive d'argent pour accumulateurs alcalins
US20080038630A1 (en) * 2005-03-25 2008-02-14 Michael Cheiky Rechargeable AgO cathode

Family Cites Families (80)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8003A (en) * 1851-03-25 Improvement in scythe-tastenings
US2528891A (en) 1945-03-26 1950-11-07 Herbert E Lawson Primary battery depolarizer and method of making the same
US3057944A (en) 1959-12-21 1962-10-09 Electric Storage Battery Co Electric battery
USRE25608E (en) 1959-12-21 1964-06-30 cahan
US3062909A (en) 1960-06-06 1962-11-06 Electric Storage Battery Co Fuel cell electrode
GB1065059A (en) 1962-12-17 1967-04-12 Electric Storage Battery Co Improvements relating to storage battery electrodes
US3325311A (en) 1964-05-19 1967-06-13 Allis Chalmers Mfg Co Preparation of a boron-doped silver oxygen electrode
US3954501A (en) 1974-01-10 1976-05-04 Guy Rampel Rechargeable electrodes utilizing unsintered fluorocarbon binder
US3920478A (en) 1974-06-25 1975-11-18 Union Carbide Corp Divalent silver oxide-zinc cell having a unipotential discharge level
US4015056A (en) 1976-03-15 1977-03-29 Esb Incorporated Method of manufacturing a stable divalent silver oxide depolarizer mix
IL50024A (en) 1976-07-12 1979-05-31 Israel State Secondary cells
JPS5380530A (en) 1976-12-24 1978-07-17 Suwa Seikosha Kk Flat battery
FR2376526A1 (fr) 1976-12-30 1978-07-28 Accumulateurs Fixes Matiere active positive pour piles electriques
US4056664A (en) 1977-01-28 1977-11-01 P. R. Mallory & Co. Inc. Electrochemical cell having an AgO electrode discharging at an Ag2 O voltage level
US4078127A (en) 1977-04-21 1978-03-07 Esb Incorporated Additive for an alkaline battery employing divalent silver oxide positive active material
JPS5937546B2 (ja) 1977-06-22 1984-09-10 松下電器産業株式会社 アルカリ電池
CA1127707A (fr) 1978-03-30 1982-07-13 Union Carbide Corporation Additif a base d'aluminium pour piles a electrodes en oxyde d'argent bivalent
US4298506A (en) 1978-11-03 1981-11-03 Duracell International Inc. Method of treating silver oxide powder and the product formed therefrom
DE3069742D1 (en) 1979-06-26 1985-01-17 Lucas Ind Plc Zinc electrode for secondary electrochemical cells and electrochemical cells including said electrode
JPS56149771A (en) 1980-04-19 1981-11-19 Hitachi Maxell Ltd Silver-oxide secondary battery
US4327157A (en) 1981-02-20 1982-04-27 The United States Of America As Represented By The Secretary Of The Navy Stabilized nickel-zinc battery
JPS58119156A (ja) 1982-01-11 1983-07-15 Seiko Instr & Electronics Ltd 過酸化銀電池
JPS58152373A (ja) 1982-03-05 1983-09-09 Seiko Instr & Electronics Ltd 過酸化銀電池
JPS59132567A (ja) 1983-01-20 1984-07-30 Seiko Instr & Electronics Ltd 過酸化銀電池
JPS59184459A (ja) 1983-04-01 1984-10-19 Sumitomo Metal Mining Co Ltd 過酸化銀電池
US4465747A (en) 1983-06-29 1984-08-14 Union Carbide Corporation Alkali metal or alkaline earth metal compound additive for manganese dioxide-containing nonaqueous cells
US4835077A (en) 1986-02-05 1989-05-30 Rayovac Corporation AgO cathode material
US6287432B1 (en) 1987-03-13 2001-09-11 The Standard Oil Company Solid multi-component membranes, electrochemical reactor components, electrochemical reactors and use of membranes, reactor components, and reactor for oxidation reactions
US5240793A (en) 1988-12-07 1993-08-31 Grillo-Werke Ag Alkaline batteries containing a zinc powder with indium and bismuth
JPH03119653A (ja) * 1989-10-02 1991-05-22 Matsushita Electric Ind Co Ltd 酸化銀電池の製造法
US5017446A (en) 1989-10-24 1991-05-21 Globe-Union Inc. Electrodes containing conductive metal oxides
US5336384A (en) 1991-11-14 1994-08-09 The Dow Chemical Company Membrane-electrode structure for electrochemical cells
HU914046D0 (en) 1991-12-19 1992-04-28 Environmetal Batteries Systems Cylindrical alkaline manganese dioxide zinc cell with improved lower sealing
HUT67932A (en) 1991-12-19 1995-05-29 Environmental Batteries System Alkaline manganese dioxide cell of low mercury content or withot mercury
DE69303091T2 (de) 1992-03-26 1997-01-23 Japan Vilene Co Ltd Batterieseparator und Batterie
US5558680A (en) 1992-11-23 1996-09-24 Wilson Greatbatch Ltd. Preparation of silver vanadium oxide cathodes utilizing sol-gel technology
JP3445654B2 (ja) 1993-03-17 2003-09-08 ウィルソン グレイトバッチ リミテッド 電気化学電池およびそのカソード
US5516340A (en) 1993-03-17 1996-05-14 Wilson Greatbatch Ltd. Process for making a metal oxide composite cathode material for high energy density batteries
US6001508A (en) 1993-06-14 1999-12-14 Rayovac Corporation AgO cathode battery
US5389469A (en) 1993-06-14 1995-02-14 Rayovac Corporation AgO battery, and material
US5393617A (en) 1993-10-08 1995-02-28 Electro Energy, Inc. Bipolar electrochmeical battery of stacked wafer cells
JPH07302597A (ja) 1994-04-29 1995-11-14 Mine Safety Appliances Co リチウム電池
US5525444A (en) 1994-06-27 1996-06-11 Toshiba Battery Co., Ltd. Alkaline secondary battery
US5599644A (en) 1995-06-07 1997-02-04 Eveready Battery Company, Inc. Cathodes for electrochemical cells having additives
US5837402A (en) 1995-12-21 1998-11-17 Dowa Mining Co., Ltd. Zinc powders for use in batteries and a secondary alkaline zinc battery using said zinc powders
JP3703582B2 (ja) 1996-02-22 2005-10-05 呉羽化学工業株式会社 電極バインダー、電極バインダー溶液、電極合剤、電極構造体および電池
US5981105A (en) 1996-07-08 1999-11-09 Emf Systems, Inc. High rate metal oxide electrodes
JP2002511179A (ja) 1996-10-11 2002-04-09 マサチューセッツ・インスティテュート・オブ・テクノロジー 電池のための固体電解質、インターカレーション化合物及び電極
CA2280865C (fr) 1997-02-24 2008-08-12 Superior Micropowders Llc Procede et dispositif de production d'aerosol, produits particulaires et materiels electroniques realises a partir desdits produits
US5928811A (en) 1997-04-11 1999-07-27 Amtek Research International Llc Gas recombinant battery separator
EP0898317B1 (fr) 1997-08-22 2007-03-21 Wilson Greatbatch Ltd. Cathode comprenant d'un oxyde métallique en phase mixte, procédé de fabrication et cellule électrochimique pour la mise en oeuvre
IL124007A (en) 1998-04-08 2001-08-26 Univ Ramot Long cycle-life alkali metal battery
JP3173594B2 (ja) 1998-08-31 2001-06-04 株式会社ファインセル マンガン塩（ｉｉ）とカ−ボン粉末を添加した硫酸亜鉛（ｉｉ）水溶液二次電池
JP2000164220A (ja) * 1998-11-26 2000-06-16 Mitsubishi Materials Corp 酸化銀電池用電極材料
US6228534B1 (en) 1998-12-21 2001-05-08 Wilson Greatbatch Ltd. Annealing of mixed metal oxide electrodes to reduce polarization resistance
JP2001185116A (ja) 1999-12-28 2001-07-06 Oji Paper Co Ltd 電池用セパレータ及びアルカリ二次電池
US6589612B1 (en) 2000-05-10 2003-07-08 The Gillette Company Battery and method of making the same
US6794082B2 (en) 2000-09-08 2004-09-21 Sony Corporation Alkaline battery
US6926999B2 (en) 2000-09-11 2005-08-09 Dowa Mining Co., Ltd. Positive electrode active material for alkaline cell
FR2817076A1 (fr) 2000-11-20 2002-05-24 Atofina Poudre microcomposite a base d'un electroconducteur et d'un fluoropolymere et objets fabriques avec cette poudre
US6797019B2 (en) 2000-12-15 2004-09-28 Wilson Greatbatch Ltd. Electrochemical cell having an electrode of silver vanadium oxide coated to a current collector
US6677070B2 (en) 2001-04-19 2004-01-13 Hewlett-Packard Development Company, L.P. Hybrid thin film/thick film solid oxide fuel cell and method of manufacturing the same
US7501208B2 (en) 2001-06-01 2009-03-10 Eveready Battery Company, Inc. Doped manganese dioxides
US7214443B2 (en) 2002-02-12 2007-05-08 Plurion Limited Secondary battery with autolytic dendrites
US6803151B2 (en) 2002-02-21 2004-10-12 Delphi Technologies, Inc. Electrode
JP4262475B2 (ja) * 2002-12-27 2009-05-13 三菱化学株式会社 非水系リチウムイオン二次電池用の負極材料及び負極、並びに非水系リチウムイオン二次電池
US7132062B1 (en) 2003-04-15 2006-11-07 Plasticolors, Inc. Electrically conductive additive system and method of making same
US7201888B2 (en) 2003-10-07 2007-04-10 Ferro Corporation Nanosized silver oxide powder
JP4809592B2 (ja) 2004-06-02 2011-11-09 株式会社豊田中央研究所 アルカリ電池用の正極活物質の製造方法
US7300722B2 (en) 2005-04-11 2007-11-27 The Gillette Company Lithium battery containing bismuth metal oxide
US7771782B2 (en) 2005-07-29 2010-08-10 Intercast Europe, srl Method of manufacturing a high impact polarized optical element and polarized optical element including an integrally bonded polarizing film
KR100668353B1 (ko) 2006-02-07 2007-01-12 삼성에스디아이 주식회사 금속 촉매 및 이를 포함한 전극을 채용한 연료전지
US7972726B2 (en) * 2006-07-10 2011-07-05 The Gillette Company Primary alkaline battery containing bismuth metal oxide
WO2008120162A2 (fr) 2007-04-02 2008-10-09 Koninklijke Philips Electronics N.V. Source d'énergie électrochimique et dispositif électronique pourvu d'une telle source d'énergie électrochimique
WO2009120352A1 (fr) 2008-03-27 2009-10-01 Zpower, Inc. Électrodes améliorées et leur emploi dans des cellules électrochimiques
US8936775B2 (en) 2008-10-29 2015-01-20 Zpower, Llc Cathode active material (higher oxides of silver)
EP2411563B1 (fr) 2009-03-27 2018-02-07 ZPower, LLC Cathode améliorée
EP2619830B1 (fr) 2010-09-24 2016-06-08 ZPower, LLC Cathode
WO2012061449A1 (fr) 2010-11-03 2012-05-10 Zpower, Llc Nouvelles électrodes et batteries rechargeables
WO2014052533A1 (fr) 2012-09-27 2014-04-03 Zpower, Llc Cathode

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4167609A (en) * 1978-03-30 1979-09-11 Union Carbide Corporation Zinc oxide additive for divalent silver oxide electrodes
JPS60189164A (ja) * 1984-03-06 1985-09-26 Matsushita Electric Ind Co Ltd 酸化銀電池
US20030207173A1 (en) * 2002-05-06 2003-11-06 Francis Wang Alkaline cell with improved cathode
US20080038630A1 (en) * 2005-03-25 2008-02-14 Michael Cheiky Rechargeable AgO cathode
WO2008004105A1 (fr) * 2006-07-05 2008-01-10 S.C.P.S. Société de Conseil et de Prospective Scientifique S.A. Nouvelle électrode positive d'argent pour accumulateurs alcalins

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8936775B2 (en) 2008-10-29 2015-01-20 Zpower, Llc Cathode active material (higher oxides of silver)
US9209454B2 (en) 2009-03-27 2015-12-08 Zpower, Llc Cathode
US20130216901A1 (en) * 2010-09-24 2013-08-22 Zpower, Llc Cathode
US9401509B2 (en) * 2010-09-24 2016-07-26 Zpower, Llc Cathode
US9184440B2 (en) 2010-11-03 2015-11-10 Zpower, Llc Electrodes and rechargeable batteries
CN103545535A (zh) * 2012-07-11 2014-01-29 丰田自动车株式会社 用于金属-空气电池的空气电极和金属-空气电池
WO2014052533A1 (fr) * 2012-09-27 2014-04-03 Zpower, Llc Cathode
US9799886B2 (en) 2012-09-27 2017-10-24 Zpower, Llc Cathode with silver material and silicate dopant and method of producing

Also Published As

Publication number Publication date
EP2497138A1 (fr) 2012-09-12
JP2013510390A (ja) 2013-03-21
EP2497138B1 (fr) 2016-06-08
JP5806675B2 (ja) 2015-11-10
US9184444B2 (en) 2015-11-10
US20130071744A1 (en) 2013-03-21
TW201128840A (en) 2011-08-16
CA2779090A1 (fr) 2011-05-12
TWI509867B (zh) 2015-11-21

Similar Documents

Publication Publication Date Title
US9184444B2 (en) Electrodes and rechargeable batteries
US9184440B2 (en) Electrodes and rechargeable batteries
JP2013510390A5 (fr)
US9209454B2 (en) Cathode
DK2901516T3 (en) cathode
US9401509B2 (en) Cathode
EP1779449A2 (fr) Pile alcaline primaire contenant de l'oxyde metallique de bismuth
US20150303461A1 (en) Composite materials for rechargeable zinc electrodes
WO2008007288A2 (fr) Piles alcalines primaires contenant un oxyde de bismuth métal
EP1668724A2 (fr) Pile alcaline primaire contenant de l'oxyde metallique de bismuth
CN113851738A (zh) 一种可充电锰离子电池及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10776246

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2779090

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2012537205

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2010776246

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 13504986

Country of ref document: US